CN1121466C - Hot melt adhesive with high peel and shear strengths for nonwoven applications - Google Patents

Hot melt adhesive with high peel and shear strengths for nonwoven applications Download PDF

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Publication number
CN1121466C
CN1121466C CN98804665A CN98804665A CN1121466C CN 1121466 C CN1121466 C CN 1121466C CN 98804665 A CN98804665 A CN 98804665A CN 98804665 A CN98804665 A CN 98804665A CN 1121466 C CN1121466 C CN 1121466C
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Prior art keywords
weight
melt adhesive
polybutene
adhesive composition
composition
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CN1254361A (en
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玛格丽特·M·弗拉利奇
马克·阿尔珀
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Bostik Inc
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Ato Findley Inc
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/18Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C09J123/20Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L57/00Compositions of unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C08L57/02Copolymers of mineral oil hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • C08L91/06Waxes

Abstract

A polybutylene based hot melt adhesive composition having a variety of end uses, particularly in construction and elastic attachment applications for nonwoven articles such as disposable diapers. Unlike typical hot melt adhesives, the present composition can withstand high peel and shear loads at elevated temperatures for extended periods of time without experiencing catastrophic bond failure. The composition includes polybutylene polymer or a mixture of polybutylene and polyolefin polymers, and a stabilizer, with the remaining ingredients chosen from one or more of a polyolefin polymer, a tackifier resin, a plasticizer, or a wax. The hot melt adhesive composition can be applied using common application techniques such as extruding or spraying.

Description

The nonwoven fabric hotmelt of high-peeling strength and high shear strength
Background of invention
The present invention relates to hot-melt adhesive composition, more specifically, the present invention relates to be used for nonwoven fabric disposable absorbent article such as diaper, based on the hotmelt of polybutene.
The disposable absorbent article of many types is that commodity can get, and they are used for absorbing and holding and stay bodily exudate, as urine and movement.The exemplary of this goods is disposable diapers for baby and supplies incontinent adult to use underwear.Typically, hotmelt just is used for the structure of these kind disposable goods.
Although many hot-melt adhesive compositions are known and are used for the structure of disposable product, be used for bonding hotmelt in a kind of concrete occasion, for other is used, may be unaccommodated fully, this also is known.Therefore, various hot-melt adhesive composition is used for the structure of disposable product.For example, people know the structure that is applicable to diaper based on polyolefinic hotmelt, particularly in the production of this goods polyolefin film etc. are bonded on tulle or the nonwoven fabric matrix.Yet people also know, are not suitable for flexible tie in the bonding diaper based on polyolefinic tackiness agent, and this is because be unaccommodated based on characteristic on the polyolefinic adhesive application such as sprayability for this application.Owing to this reason, the segmented copolymer of styrene-based system is used in during elastic adhesive uses as the hotmelt of styrene-isoprene-phenylethene (SIS) segmented copolymer or styrene-butadiene-styrene (SBS) segmented copolymer.Yet these styrene block copolymer tackiness agents also have some shortcoming, as the viscosity unstable that shows under at comparatively high temps.
More importantly; usually based on the shortcoming of the hotmelt of SIS and SBS, in using, nonwoven fabric shows this application need seam especially significantly; adhere on the diaper as elastic sides, or functional bur such as restraint zone bond on the disposable diaper.These assemblies often need under high peel stress and/or shearing force, work under the body temperature temperature in long-time.Under such situation, the stripping strength of common tackiness agent and shear strength are not enough.As a result, typically, these application scenarios need mechanical connection, as ultrasonic welding or mechanical connection and the combination of tackiness agent auxiliary phase.Yet it is expensive usually to be used for these equipment of using, needs to safeguard frequently, and has limited production rate.
Summary of the invention
The present invention relates to have certain physicals, make it can be ideally suited for the hot-melt adhesive composition of nonwoven fabric disposable product.More specifically, when under the higher temperature in the long time, be subjected to very harsh peel off and/or during shearing action, hotmelt of the present invention has kept acceptable bonding strength.Therefore tackiness agent of the present invention is applicable to the nonwoven fabric application, and this application depends on MACHINERY JOINT or mechanical connection and the combination of tackiness agent auxiliary phase at present.The viscosity of tackiness agent of the present invention under 177 ℃ (350) is less than 25000cP, and fusing point is higher than 121 ℃ (250 °F).
Hot-melt adhesive composition of the present invention is specially adapted in the application of disposable non-woven textile article such as diaper or water conservancy diversion trousers.Especially, this binder composition is applicable to the laminate of bonding various elasticity or non-elastic material.More particularly, this tackiness agent can be used for the elastic diaper side is bonded to various matrix, as nonwoven fabric, polyethylene, polypropylene etc.
When carrying out the standard peel strength test, hot-melt composition of the present invention also has good structure cementability.In addition, these tackiness agents also have and make it be easy to the physicals of processing on common hot melt equipment.
Hot-melt adhesive composition of the present invention contains the mixture of following component:
(a) polybutene homopolymer or the multipolymer of about 15~65 weight %;
(b) stablizer of about 0.1~3 weight %; And
According to concrete end-use and desired properties, one or more that remaining ingredient is selected from following component make weight based on whole composition, each components contents and be 100%:
(c) polyolefin polymer of about 0~70 weight %;
(d) tackifying resin of about 0~60 weight %;
(e) softening agent of about 0~30 weight %; With
(f) wax of about 0~20 weight %.The minimum content of polybutylene polymer should be about 15 weight % in the described composition.
In long period, under the comparatively high temps, extreme peel off with shearing action under can provide enough bonding strengths, the preferred hot-melt adhesive composition of plasticizer-containing is not made up of the mixture of following component:
(a) the polybutene homopolymer of about 19.9 weight %;
(b) tackifying resin of about 29.9 weight %;
(c) polyolefin copolymer of about 39.8 weight %;
(d) polyethylene wax of about 9.5 weight %; With
(e) stablizer of about 0.9 weight %.
Another not the hot-melt adhesive composition of plasticizer-containing form by the mixture of following component:
(a) the polybutene homopolymer of about 25 weight % and the blend of multipolymer;
(b) tackifying resin of about 25 weight %;
(c) wax of about 19.5 weight %;
(d) polyolefin polymer of about 30 weight %; With
(e) stablizer of about 0.5 weight %.
Not the content of wax and plasticizer-containing can not provide simultaneously hot-melt adhesive composition enough bonding strengths, preferred to form by the mixture of following component:
(a) the polybutene homopolymer of about 20 weight %;
(b) tackifying resin of about 30 weight %;
(c) polyolefin copolymer of about 29 weight %;
(d) stablizer of about 1 weight %; With
(e) polybutene copolymer of about 20 weight %.
Under the comparatively high temps, extreme peel off with shearing action under can provide preferred hot-melt adhesive composition enough bonding strengths, that do not contain polyolefin polymer to form by the mixture of following component:
(a) polybutene copolymer of about 50 weight %;
(b) tackifying resin of about 15 weight %;
(c) softening agent of about 15 weight %;
(d) wax of about 19.5 weight %; With
(e) stablizer of about 0.5 weight %.
Do not contain tackifying resin or polyolefin polymer, simultaneously under comparatively high temps, extreme peel off with shearing action under the preferred hot-melt adhesive composition of enough bonding strengths can be provided, form by the mixture of following component:
(a) polybutene copolymer of about 65 weight %;
(b) wax of about 19.5 weight %;
(c) softening agent of about 15 weight %; With
(d) stablizer of about 0.5 weight %.
Therefore hot-melt adhesive composition of the present invention can provide under comparatively high temps in a long time and have good resistance and peel off bonding with shearing force, and to the mechanical connection in the nonwoven fabric disposable product, particularly the mechanical connection of laminate provides another kind of selection mode.The preferred adhesive composition that is mixed with can tolerate down minimum about 11 hours of the stress of the forms of peeling off of 500 grams at 38 ℃ (100 °F), and can tolerate minimum about 11 hours of the stress of the shear-forms of 1000 grams down at 38 ℃ (100 °F).
Description of drawings
In the accompanying drawing:
Fig. 1 is explanation according to the hotmelt of the present invention preparation bar graph with respect to the stripping strength of the hotmelt of prior art; And
Fig. 2 is explanation according to the hotmelt of the present invention preparation bar graph with respect to the shear strength of the hotmelt of prior art.
Detailed Description Of The Invention
In the adhesive-bonded fabric disposable product, when estimating high shear and high when peeling off the lower bonding strength of service condition, have the hot-melt adhesive composition based on polybutene of following constituent content, compare with the hotmelt of prior art and have advantage. More specifically, based on the gross weight of composition, this adhesive composition contains polybutene homopolymers or the copolymer of 15~65 % by weight of having an appointment. The minimum content of polybutylene polymer should be about 15 % by weight in the composition. According to final use and desired properties, can not have polyolefin component, but typically, its content is about 0~70 % by weight. Hotmelt of the present invention also contains the stabilizing agent of 0.01~3 % by weight of having an appointment, and according to final use and desired properties, also selectively contains 0~60% the tackifying resin of having an appointment, the plasticizer of about 0~30 % by weight, or the wax of about 0~20 % by weight. Each component must consist of 100 % by weight of composition, and percentage described here is based on the weight of whole adhesive composition yet significantly.
In thermoplastic hot melt adhesive composition of the present invention, using polybutene component is for the bonding connection intensity that improves material under higher temperature, particularly makes composition have high-peeling strength and high shear strength. Terminology used here " polybutylene polymer " refers to contain ethene and butene monomers, and butene monomer units consists of those polymer of at least 89% of copolymer. Suitable commercially available butene-1-ethylene copolymer can be from Shell Chemical Company of Houston, Texas, bought with trade name Duraflex 8910PC or Duraflex 8510, perhaps suitable homopolymers is DP 0800, also can buy from Shell Chemical Company. The DSC fusing point of preferred material is about 90 ℃ or higher. Based on the gross weight of composition, although the amount of spendable polybutylene polymer is 15~65 % by weight, its preferred use amount is 20~50 % by weight.
Be applicable to that butene-1 homopolymers of the present invention and copolymer are ethyl side groups molecule regular union space ordered arrangement, that be mainly straight chain. These side groups are to form during at the two key places of 1,2-carbon and along the polymerization of ethylene chain main chain when butene-1. This is disclosed in patent US3362940 in further detail. When by melt cooling, these ethyl side groups are to locate at the quadrangle space arrangement at first. As time goes on, quadrangle crystalline phase formal transformation is stable hexagon space arrangement, and physical property makes moderate progress thereupon. The patent US4937138 that authorizes Mostert is seen in the more detailed description of relevant polymer described here, and the content of this patent is drawn here and is reference. Can be found out that by above-mentioned the Optimum of this polymer is about 15~65 % by weight.
Amorphous polyolefin polymers compositions in the present composition is preferably the poly alpha olefin copolymer based on the copolymer of ethene, propylene, butylene and hexene repetitive. They can be made of the alternately repetitive of following combination of monomers:
(a) ethene and propylene;
(b) ethene and butylene;
(c) propylene and butylene;
(d) ethene, propylene and butylene;
(e) propylene and hexene; Or
(f) propylene.
Suitable copolymer can be from Huls America with trade name " Vestoplas ", or has bought with trade name " Rextac " from Rexene Products. Preferred softening point is about 100~160 ℃ copolymer. Should be realized that any mixture of above-mentioned copolymer also can be used as matrix component in composition of the present invention. The effect of polyolefin polymer is to help to provide cementability at no pore matrix. Based on the gross weight of composition, although the use amount of polyolefin polymer can be 0~70 % by weight, preferred amount is 20~40 % by weight.
Should be noted in the discussion above that the mixture that also can use polybutylene polymer and polyolefin polymer, condition is to have used the polybutylene polymer of q.s to give peeling off and shear strength of adhesive composition aequum. The minimized content of polybutylene polymer should be about 15% in the composition. Yet according to final use, and as aforementioned range was pointed, polyolefin component can not exist in composition fully.
The tackifying resin that is used for hot melt structure adhesive of the present invention is to strengthen bond properties and improve polybutene copolymer and/or the material of the specific adhesion of poly alpha olefin copolymer. Terminology used here " tackifying resin " comprising:
(a) rosin of natural and modification, for example resin, wood rosin, Starex, distillation rosin, Foral, dimerization colophonium and newtrex;
(b) glyceride and the pentaerythritol ester of natural and modified rosin, the glyceride of light wood rosin for example, the glyceride of Foral, the glyceride of newtrex, the pentaerythritol ester of light color wood rosin, the pentaerythritol ester of Foral, the phenol-modified pentaerythritol ester of the pentaerythritol ester of Starex and rosin;
(c) softening point of measuring according to the method for ASTM E28-58T is about 60~140 ℃ polyterpene resin, the latter's polyterpene resin normally by terpene hydrocarbon as being called the monoterpene of firpene, what polymerization obtained in the presence of Friedel-Crafts catalyst under the suitable low temperature; The polyterpene resin that also comprises hydrogenation;
(d) copolymer of natural terpenes and terpolymer, styrene/terpene for example, AMS/terpenes, and vinyltoluene/terpenes;
(e) phenol-modified terpene resin, the resin product that for example in acid medium, is obtained by the condensation of terpenes and phenols;
(f) ring and ball softening point is about 60~140 ℃ aliphatic petroleum hydrocarbon resin, and this resin is obtained by the polymerization of the monomer that mainly is made up of alkene and alkadienes; Also include the aliphatic petroleum hydrocarbon resin of hydrogenation; This class is based on C5The commercially available example of the resin of-olefine fraction is " Wingtack 95 " and " Wingtack 115 " distillation tackifying resin, is sold by Goodyear Tire and Rubber Company;
(g) aromatics petroleum hydrocarbon and hydrogenated derivatives thereof;
(h) aliphatic series/aromatics petroleum derivation hydrocarbon and hydrogenated derivatives thereof.
The mixture that for some prescription, may need above-mentioned two or more tackifying resins. Although the amount ranges of spendable tackifying resin is 10~60 % by weight, preferable range is 20~50 %.
As mentioned above, the amount that is applicable to the tackifying resin in the scope of the invention accounts for the about 0~60% of whole composition weights, and when it was used in the composition, its content was preferably about 10~30% of composition weight. Preferably, tackifying resin is selected from any nonpolar type that can buy. The example that is applicable to tackifying resin of the present invention that can buy comprises the commercial resin that is indicated by trade name Escorez, and it is produced by Exxon Chemical Company. Can be used for resin that another kind of the present invention can buy and be the resin of the commodity " Eastotac " by name that can buy from Eastman Chemical Company. Usually, be applicable to nonpolar tackifying resin of the present invention, comprise partially or completely hydrogenation, based on C9Or C5Hydrocarbon, softening point range is about 10~125 ℃ resin. Can be used for tackifying resin of the present invention and also can comprise the polarity tackifying resin. Yet because many polar resins are only partly compatible with butene-1 homopolymers and copolymer, therefore the selection of utilizable polar resin is limited.
For the control of required viscosity is provided, also selectively comprise plasticizer in the composition of the present invention, based on the weight of whole composition, its amount is preferably about 5~15% for about 0~30%. Suitable plasticizer not only comprises plasticizer oil commonly used, such as mineral oil, also comprise olefin oligomer and low-molecular weight polymer (as molecular weight be 2000 or littler low-molecular-weight polybutene), and the derivative of vegetable oil and animal oil and this class oil. Spendable petroleum derived oils is for only containing the relatively high boiling material of a small amount of aromatic hydrocarbons. Based on this point, aromatic hydrocarbons should preferably less than 30% of weight of oil, be more preferably less than 15 %. Or this oil can be does not have aromatic hydrocarbons fully. Oligomer can be that mean molecule quantity is about 350~10000 polypropylene, polybutene, the polyisoprene of hydrogenation, the polybutadiene of hydrogenation etc. Suitable vegetable oil and animal oil comprise glyceride and the polymerizate thereof of aliphatic acid commonly used. Be applicable to that plasticizer of the present invention can be many different plasticizer, but the inventor finds, containing just like the monoolefine polymer that can buy commodity Indopol H-100 by name (it is the monoolefine polymer based on butylene of being produced by Amoco company) and its molecular weight is 2000 or lower plasticizer, is specially adapted to the present invention. As is understood, typically, the use of plasticizer is in order to reduce the viscosity of whole adhesive composition, and does not basically reduce the serviceability temperature of adhesive. Yet if used plasticizer in the composition, the use amount that must increase polybutene keeps the required high-peeling strength of these adhesives with the compensation plasticizer.
Can 0~20 % by weight, the consumption of preferred 5~20 % by weight is used for the wax of the present composition, under the prerequisite of not obvious reduction polymer adhesive feature, can be used to reduce the melt viscosity of hot melt structure adhesive. Under the prerequisite that does not affect temperature performance, these can also be used to reduce the die sinking time (open time) of composition. The wax that is suitable for is:
(1) molecular weight is 1000~6000 low molecular weight polyethylene, and its hardness number of being measured by the method for ASTM D-1321 is about 0.1~120, and the ASTM softening point is about 66~121 ℃ (150~250 °F);
(2) pertroleum wax is the paraffin of about 54~80 ℃ (130~175 °F) such as fusing point, and fusing point is the microwax of about 57~93 ℃ (135~200 °F), and latter's fusing point is to be measured by the method for ASTM D127-60;
(3) ring and ball softening point is about 120~160 ℃ random polypropylene;
(4) synthetic wax that obtains of the polymerization by carbon monoxide and hydrogen is such as Fischer-Tropsch wax; With
(5) polyolefin-wax. Terminology used here " polyolefin-wax " refers to those polymer or the long-chain material that are made of olefin monomer unit such as ethene or propylene. These materials can be from Eastman Chemical Co., and " Epolene " bought with trade name. Being preferred for the ring and ball softening point that this class material in the present composition has is 93~177 ℃ (200~350 °F). Should be understood that each in these wax dilutions at room temperature is solid. Other this class material that is suitable for comprises animal, fish and plant fat and the oil of hydrogenation, such as the tallow of hydrogenation, lard, soya-bean oil, cotton seed oil, castor oil, pilchardine, cod-liver oil etc., owing to be hydrogenated them and be at ambient temperature solid, finds that above-mentioned these also are suitable for to do the alternative of wax dilution. The material of these hydrogenations often is called " animal or plant wax " in adhesives industry.
Comprise stabilizing agent among the present invention, its consumption is about 0.1~3 % by weight, but is preferably about 0.1~1 % by weight. Be used in combination the stabilizing agent that is applicable to hot-melt adhesive composition of the present invention; help to protect above-mentioned polymer and total adhesive composition; avoid it to be subjected to the common heat that in adhesive production and use procedure, takes place and the impact of oxidative degradation, and final products are exposed to the impact of surrounding environment usually. This degraded usually variation of outward appearance, physical property and the operating characteristic by adhesive shows. The stabilizing agent that is suitable for is hindered phenol and the polyfunctional phenol of HMW, as contains the phenol of sulphur and phosphorus. Hindered phenol is known to the one skilled in the art, it is characterized in that at the phenolic compound that also contains the bigger group of spatial volume near the position of phenolic hydroxyl group. Particularly, usually replace at least one ortho position of the phenolic hydroxyl group of phenyl ring the tert-butyl group is arranged. The effect that reduces its elongation frequency has been played in the existence of the substituted radical that near these spatial volumes hydroxyl are bigger, and has therefore reduced its reactivity; Therefore this sterically hindered effect makes phenolic compound have stability. The representative example of sterically hindered phenol comprises:
1,3,5-trimethyl-2,4,6-three (3,5-di-tert-butyl-4-hydroxyl benzyl) benzene;
Pentaerythrite four-3 (3,5-di-tert-butyl-hydroxy phenyl) propionic ester;
N-octadecane base-3 (3,5-di-tert-butyl-hydroxy phenyl) propionic ester;
4,4 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert-butylphenol);
4,4 '-thiobis (the 6-tert-butyl group-neighbour-cresols);
2,6-DI-tert-butylphenol compounds;
6-(4-hydroxyphenoxy)-2, two (n-octadecane base the sulfo-)-1,3,5-triazines of 4-;
2,4,6-three (4-hydroxyl-3,5-di-t-butyl-phenoxy group)-1,3,5-triazines;
Two-n-octadecane base-3,5-di-tert-butyl-4-hydroxyl benzyl phosphate;
2-(n-octyl sulfo-) ethyl-3,5-di-tert-butyl-4-hydroxybenzoic acid ester; With
Sorbitol Powder six-(3,3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester.
Particularly preferred stablizer is tetramethylolmethane four-3 (3, a 5-di-tert-butyl-hydroxy phenyl) propionic ester.
The performance of these stablizers can further strengthen by being used in combination following substances: (1) synergist, as thiodipropionate and phosphorous acid ester; (2) sequestrant and metal deactivator are as ethylenediamine tetraacetic acid (EDTA) and salt and salicyl salicylic acid diplosal propylene diimine.
Can use any technique known in this area that hot-melt adhesive composition of the present invention is prepared.An exemplary of prior art is included in one is furnished with in the mixing kettle of strap clamp cover of agitator, preferably put into all materials in the large vol mixing tank of a Baker-Perkins or Day type strap clamp cover, the temperature with this mixture rises to about 121~190 ℃ (250~375 °F) subsequently.Should be understood that employed precise temp will depend on the fusing point of concrete component in this step.Stir the binder composition of gained, dissolve fully until each component.Remove any air that enters by vacuum then.
Should be understood that,, can in binder composition of the present invention, add the additive of other selection for improving specific physicals.These additives can comprise, for example material such as tinting material, filler.
So just formed according to product of the present invention, it on the porous matrix under higher temperature, can tolerate and shear and peel stress.Can use these tackiness agents by method commonly used, comprise contact and non-contacting, they are softish and tack-free when solidified.For making performance performance enough abundant, now to measure, these tackiness agents must can tolerate minimum about 11 hours of the peeling force of per inch 500g down at 38 ℃ (100 °F), tolerate minimum about 11 hours of the shearing force of 1000g under 38 ℃ (100 °F).This finishes with mechanical connection matrix by formation is resistance to deformation.Although the viscosity than common combinations thing is higher slightly, these new tackiness agents still can easily be processed by the use equipment of standard, and keeping the high-intensity while, have enough toughness.High-shear-Gao peels off the test condition of batching
Laminar construction: in this test, the matrix of selection must have enough intensity to support specified load.To fulfill this requirement, be configured to a kind of nonwoven fabric/polyethylene film lamination thing, it can keep its shape under the load of 38 ℃ (100), 1000g/in.This is by using from (the Ato Findley of Ato Findley Inc., Inc.) the high-strength hot melt adhesive that bought, styrene-based based block copolymer (SIS), that commodity can get, the nonwoven fabric that unit weight is heavier are laminated to and make on the polyethylene film.
Bonding application: with spiral spray into 3/8 inch wide, 15 milligrams form is applied to all tackiness agents on nonwoven fabric one side of above-mentioned laminate per square inch.The die sinking time of this application is 0.5 second, and use temperature is 1 77 ℃ (350 °F).Use 9 pounds/square inch roll-in to make second laminate and nonwoven fabric side form bonding.
High temperature test: all samples were placed minimum 24 hours.Perpendicular to spiral direction, sample is cut into 1 inch wide length.Hang over then in the circulated air oven of 38 ℃ (100) sample is tested.
Static state is peeled off test: with the common test mode of peeling off the weight of 500g is adhered on each sample, and pick up counting.Minute to note each sample to bond failure time institute elapsed time.For each batching, test minimum 5 samples.For reaching acceptable degree, sample must continue 11 hours, or 660 minutes.
Static shear test: adhere on each sample with the weight of common shearing test mode, and pick up counting with 1000g.Minute to note each sample to bond failure time institute elapsed time.For each batching, test minimum 5 samples.For reaching acceptable degree, sample must continue 11 hours, or 660 minutes.
The present invention is further illustrated by following embodiment.
Embodiment 1
Prepare following binder blend according to the present invention.During test, this tackiness agent provides the enough form of peeling off and the bonding strength of shear-form under higher temperature, and performance is very excellent.Owing to used polybutene homopolymer, the amorphous poly-alpha-olefines of high softening-point and the tackifier of high softening-point, the general class name 29.9 Eastotac H-130R Eastman Chemical Company resins of the sample of present embodiment has good high-temperature intensity. % by weight component merchandise resources 19.9 polybutene DP 0800 Shell Chemical Company polybutene 39.8 Rextac 2115 Rexene Products polyolefin 9.5 Epolene N15 Eastman Chemical Company waxes 0.9 Irganox 1010-FF Ciba Addit ives stabilizing agent embodiment 2
This Example formulations of the present invention is the content of wax not.Present embodiment has used the tackifier and the unbodied poly-alpha olefins of high softening-point, and the mixture of polybutene homopolymer and polybutene-ethylene copolymer.Do not use wax in this prescription, therefore improved viscosity, but made this batching have bigger toughness, and had the longer die sinking time than embodiment 1.The general class name of weight % component merchandise resources
30 Eastotac H-130R Eastman Chemical Company resins
20 polybutene DP, 0800 Shell Chemical Company polybutene
29 Rextac, 2115 Rexene Products polyolefine
20 polybutene DP, 8910 Shell Chemical Company polybutene
1 Irganox 1010-FF Ciba Additives stablizer
Embodiment 3
Prescription in this embodiment of the invention has used the polybutene softening agent to replace amorphous poly-alpha-olefines.In addition, the general class name 15 Eastotac H-100W Eastman Chemical Company resins of it uses polybutene-ethylene copolymer. % by weight component merchandise resources 50 polybutene DP 8910 Shell Chemical Company polybutene 15 Indopol H100 Amoco plasticizer 19.5 Epolene N15 Eastman Chemical Company waxes 0.5 Irganox 1010-FF Ciba Additives stabilizing agent
Embodiment 4
This prescription contains the mixture of polybutene homopolymer and polybutene-ethylene copolymer, the general class name 25 Eastotac H-100W Eastman Chemical Company resins of and the amorphous poly-alpha-olefines of the tackifier of low softening point and low softening point. % by weight component merchandise resources 12.5 polybutene DP 0800 Shell Chemical Company polybutene 12.5 polybutene DP 8910 Shell Chemical Company polybutene 19.5 Epolene N15 Eastman Chemical Company waxes 0.5 Irganox 1010-FF Ciba Additives stabilizing agent 30 Rextac 2715 Rexene Products polyolefin
Embodiment 5
This Example formulations of the present invention does not contain tackifying resin.On some porous matrix, mechanical connection is bonding more important than stromal surface.Under these situations, can flow into the interior batching of porous matrix in the substrate, and form the mechanical connection of antistripping and shear-stress " locking ".Therefore it is bonding not need tackifying resin to promote.This prescription is the mixture of polybutene softening agent, Poly Propylene Wax and polybutene-ethylene copolymer.The general class name 65 polybutene DP of weight % component merchandise resources 8910 Shell Chemical Company polybutene
Polybutene 15 Indopol H100 Amoco softening agent 19.5 Epolene N15 Eastman Chemical Company waxes 0.5 Irganox 1010-FF Ciba Additives stablizer reference examples 1
This prescription (being designated as " reference examples 1 ") is commodity H2104 by name, the hotmelt that can buy from Ato Findley Inc..
Typically, H2104 is used for the nonwoven fabric application of relative higher-strength of needs such as elastic adhesive.H2104 is typical case's representative of high-strength hot melt adhesive in the hotmelt type of prior art, and it typically is used for heavily stressed diaper application such as elastic adhesive.Reference examples 2
This prescription (being designated as " reference examples 2 ") is the mixture of polybutene homopolymer, high softening-point tackifier and high softening-point amorphous poly-alpha-olefines, and wherein plasticizer dosage has surpassed the indicated scope of the present invention.This product does not possess required anti-shearing or stripping performance.The general class name of weight % component merchandise resources
30 Eastotac H-130R Eastman Chemical Company resins
20 polybutene DP, 0800 Shell Chemical Company polybutene
Polybutene
35 Indopol H100 Amoco softening agent, 14.5 Vestoplast, 608 Huls Chemical Company polyolefine, 0.5 Irganox 1010-FF Ciba Additives stablizer reference examples 3
This prescription (being designated as " reference examples 3 ") contains mixture, the tackifier of medium softening temperature and the Poly Propylene Wax of high softening-point amorphous poly-alpha-olefines and high softening-point of polybutene homopolymer and poly-(butylene-ethene) multipolymer, and wherein the consumption of polybutylene polymer is less than the indicated scope of the present invention.Although this product has enough anti-shear performances and the softening temperature that can compare with embodiment 1~5, it does not possess peeling resistance required in this application.The general class name of weight % component merchandise resources
20 Escorez, 1315 Exxon Chemi cal Company resins
5 polybutene DP, 0800 Shell Chemical Company polybutene
5 polybutene DP, 8910 Shell Chemical Company polybutene
9.5 Epolene N15 Eastman Chemical Company wax
0.5 Irganox 1010-FF Ciba Additives stablizer
60 Rextac, 2115 Rexene Products polyolefine test results
Test according to aforesaid method, to determine the stripping strength and the shear strength of above-mentioned prescription, result data is listed in respectively in the table 1 electric charge table 2.The softening temperature and the viscosity of these compositions are listed in table 3 and the table 4 respectively.
Table 1
Prescription Static state peel off (minute) (mean values of 5 samples)
Reference examples 1 17
Reference examples 2 0.3
Reference examples 3 23
Embodiment 1 1000+
Embodiment 2 1000+
Embodiment 3 1000+
Embodiment 4 1000+
Embodiment 5 1000+
Table 2
Prescription Static shear (minute) (mean values of 5 samples)
Reference examples 1 29
Reference examples 2 397
Reference examples 3 1000+
Embodiment 1 1000+
Embodiment 2 1000+
Embodiment 3 1000+
Embodiment 4 1000+
Embodiment 5 1000+
Table 3
Prescription Softening temperature ℃ (°F) (Herzog ring and ball method tester)
Reference examples 1 103(217.4)
Reference examples 2 117(242.6)
Reference examples 3 155.2(311.4)
Embodiment 1 155(311)
Embodiment 2 138.7(281.7)
Embodiment 3 157.2(315)
Embodiment 4 156.8(314.3)
Embodiment 5 162.2(324)
Table 4
Prescription Viscosity (cP) under 163 ℃ (325) Viscosity (cP) under 177 ℃ (350) Viscosity (cP) under 190 ℃ (375)
Reference examples 1 4500 2700 1550
Reference examples 2 5675 3615 2465
Reference examples 3 3700 2600 1850
Embodiment 1 7300 5400 3500
Embodiment 2 31200 21050 14125
Embodiment 3 15550 10425 7250
Embodiment 4 10375 6813 4688
Embodiment 5 10625 6175 4425
Processing is compared: hotmelt must have lower viscosity, to carry out good processing on common coating apparatus.Following is that the good styrene-based of processing characteristics is typical block copolymer adhesive H2104, with the comparison based on the tackiness agent of polybutene of embodiment 1.This embodiment sample also has good processing properties.Listed temperature has been represented the typically used and/or the processing temperature of hotmelt.
Viscosity
Viscosity (cPs) 3500 under the viscosity (cPs) under the viscosity (cPs) under the viscosity (cPs) under the viscosity (cPs) under the viscosity (cPs) under the H2104 embodiment 1163 ℃ (325) 4,500 163 ℃ (325) 7300177 ℃ (350) 2,700 177 ℃ (350) 5400190 ℃ (375) 1,550 190 ℃ (375)
Thermostability H2104 sample 177 ℃ (350 °F) down embodiment 1 sample in 185 ℃ (365) 3,650 177 ℃ of (350) viscosity (cPs) 5390 viscosity variation-19% viscosity variations-0.2% down of aging 48 hours aging 48 hours 163 ℃ of (325) viscosity (cPs) down down
Data presentation, for being matched with the viscosity of H2104, the sample of embodiment 1 must be operated under higher a little temperature.Yet under typical processing temperature, two kinds of products all are easier to processing.In addition, when carrying out the long period when aging under comparatively high temps, the sample of embodiment 1 has kept its viscosity better than H2104.

Claims (6)

1, the hot-melt adhesive composition of a kind of high-peeling strength and shear strength, it is made up of the mixture of following component basically:
(a) polybutylene polymer of 15~65 weight %;
(b) stablizer of 0.1~3 weight %; And
(c) softening temperature of 5~20 weight % is 93 ℃ to 177 ℃ a Poly Propylene Wax;
Remaining ingredient is selected from one or more in the following component, makes weight based on whole composition, the weight of each component and be 100%:
(d) the hydrocarbon tackifying resin of 0~60 weight %; With
(e) it is polybutene below 2000 that the softening agent of 0~30 weight %, this softening agent are selected from mineral oil and molecular weight;
Wherein the minimized content of polybutylene polymer is 15 weight %; And this binder composition has the viscosity and the fusing point that are lower than 25000cP and is higher than 121 ℃ under 177 ℃, and minimum about 11 hours of the stress of 38 ℃ of forms of peeling off that can tolerate down 500 grams, and minimum about 11 hours of the stress of 38 ℃ of shear-forms that can tolerate 1000 grams down.
2, hot-melt adhesive composition as claimed in claim 1, wherein said polybutylene polymer is poly-(butylene-ethene) multipolymer.
3, the hot-melt adhesive composition of a kind of high-peeling strength and shear strength, it is made up of following component basically:
(a) polybutylene polymer of 65 weight %;
(b) softening temperature of 19.5 weight % is 93 ℃ to 177 ℃ a Poly Propylene Wax;
(c) it is polybutene below 2000 that the softening agent of 15 weight %, this softening agent are selected from mineral oil and molecular weight;
(d) stablizer of 0.5 weight %; With
(e) wherein this binder composition has the viscosity and the fusing point that are lower than 25000cP and is higher than 121 ℃ under 177 ℃, and minimum about 11 hours of the stress of 38 ℃ of forms of peeling off that can tolerate down 500 grams, and minimum about 11 hours of the stress of 38 ℃ of shear-forms that can tolerate 1000 grams down.
4, hot-melt adhesive composition as claimed in claim 3, wherein said polybutylene polymer is poly-(butylene-ethene) multipolymer.
5, the hot-melt adhesive composition of a kind of high-peeling strength and shear strength, it is made up of following component basically:
(a) polybutylene polymer of 50 weight %;
(b) it is polybutene below 2000 that the softening agent of 15 weight %, this softening agent are selected from mineral oil and molecular weight;
(c) the hydrocarbon tackifying resin of 15 weight %;
(d) softening temperature of 19.5 weight % is 93 ℃ to 177 ℃ a Poly Propylene Wax; With
(e) stablizer of 0.5 weight %;
(f) wherein this binder composition has the viscosity and the fusing point that are lower than 25000cP and is higher than 121 ℃ under 1 77 ℃, and minimum about 11 hours of the stress of 38 ℃ of forms of peeling off that can tolerate down 500 grams, and minimum about 11 hours of the stress of 38 ℃ of shear-forms that can tolerate 1000 grams down.
6, hot-melt adhesive composition as claimed in claim 5, wherein said polybutylene polymer is poly-(butylene-ethene) multipolymer.
CN98804665A 1997-04-30 1998-04-22 Hot melt adhesive with high peel and shear strengths for nonwoven applications Expired - Fee Related CN1121466C (en)

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EP0977820B1 (en) 2004-07-14
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JP4364311B2 (en) 2009-11-18
DE69825044T2 (en) 2005-08-25
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WO1998049249A1 (en) 1998-11-05
ES2221166T3 (en) 2004-12-16

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